Terrestrial inputs boost organic carbon accumulation in Mexican mangroves.

Despite their ability to mitigate climate change by efficiently absorbing atmospheric carbon dioxide (CO2) and acting as natural long-term carbon sinks, mangrove ecosystems have faced several anthropogenic threats over the past century, resulting in a decline in the global mangrove cover. By using standardized methods and the most recent Bayesian tracer mixing models MixSIAR, this study aimed to quantify source contributions, burial rates, and stocks of organic carbon (Corg) and explore their temporal changes (∼100 years) in seven lead-210 dated sediment cores collected from three contrasting Mexican mangrove areas. The spatial variation in Corg burial rates and stocks in these blue carbon ecosystems primarily depended on the influence of local rivers, which controlled Corg sources and fluxes within the mangrove areas. The Corg burial rates in the cores ranged from 66 ± 16 to 400 ± 40 g m-2 yr-1. The Corg stocks ranged from 84.9 ± 0.7 to 255 ± 2 Mg ha-1 at 50 cm depth and from 137 ± 2 to 241 ± 4 Mg ha-1 at 1 m depth. The highest Corg burial rates and stocks were observed in cores from the carbonate platform of Yucatan and in cores with reduced river influence and high mangrove detritus inputs, in contrast to patterns identified from global databases. Over the past century, the rising trends in Corg burial rates and stocks in the study sites were primarily driven by enhanced inputs of fluvial-derived Corg and, in some cores, mangrove-derived Corg. Despite their decreasing extension, mangrove areas remained highly effective producers and sinks of Corg. Ongoing efforts to enhance the global database should continue, including mangrove area characteristics and reliable timescales to facilitate cross-comparison among studies.

From radiometry to chronology of a marine sediment core: A 210Pb dating interlaboratory comparison exercise organised by the IAEA.

Laboratories from 14 countries (with different levels of expertise in radionuclide measurements and 210Pb dating) participated in an interlaboratory comparison exercise (ILC) related to the application of 210Pb sediment dating technique within the framework of the IAEA Coordinated Research Project. The laboratories were provided with samples from a composite sediment core and were required to provide massic activities of several radionuclides and an age versus depth model from the obtained results, using the most suitable 210Pb dating model. Massic concentrations of Zn and Cu were also determined to be used for chronology validation. The ILC results indicated good analytical performances while the dating results didn't demonstrate the same degree of competence in part due to the different experience in dating of the participant laboratories. The ILC exercise enabled evaluation of the difficulties faced by laboratories implementing 210Pb dating methods and identified some limitations in providing reliable chronologies.

Anthropogenic and natural impacts in the marine area of influence of the Grijalva - Usumacinta River (Southern Gulf of Mexico) during the last 45 years.

The development of the Grijalva-Usumacinta river basin exerts modifications on its discharge area. A sediment core was studied to reconstruct environmental changes and trace element contamination status during the past 45 years. 210Pb-derived mass accumulation rates indicate higher sediment input to the area since 1995, related to increased precipitation and floodings in the catchment area. Sediments show finer particles from the late 1970s on, likely related to dams construction upriver and/or land use changes. Heavy metal enrichment factors (EF < 2) suggest minimum contamination. Benthic foraminifera and redox-sensitive - elements (As, Ba, Co, Cr, Cu, Ni, Pb, V and Zn) indicate the sediments before 2000 were deposited under oxygenated conditions. Afterwards, environmental conditions changed and benthic foraminifera and dinocysts assemblages changed suggesting eutrophication and lower oxygen conditions during the last 20 years. Monitoring should be continued to assess eutrophication/hypoxic/pollution trends that could become deleterious to the marine biota.

Distribution of artificial radionuclides in deep sediments of the Mediterranean Sea.

Artificial radionuclides enter the Mediterranean Sea mainly through atmospheric deposition following nuclear weapons tests and the Chernobyl accident, but also through the river discharge of nuclear facility effluents. Previous studies of artificial radionuclides impact of the Mediterranean Sea have focussed on shallow, coastal sediments. However, deep sea sediments have the potential to store and accumulate pollutants, including artificial radionuclides. Deep sea marine sediment cores were collected from Mediterranean Sea abyssal plains (depth >2000 m) and analysed for (239,240)Pu and (137)Cs to elucidate the concentrations, inventories and sources of these radionuclides in the deepest areas of the Mediterranean. The activity - depth profiles of (210)Pb, together with (14)C dating, indicate that sediment mixing redistributes the artificial radionuclides within the first 2.5 cm of the sedimentary column. The excess (210)Pb inventory was used to normalize (239,240)Pu and (137)Cs inventories for variable sediment fluxes. The (239,240)Pu/(210)Pb(xs) ratio was uniform across the entire sea, with a mean value of 1.24x10(-3), indicating homogeneous fallout of (239,240)Pu. The (137)Cs/(210)Pb(xs) ratio showed differences between the eastern (0.049) and western basins (0.030), clearly significant impact of deep sea sediments from the Chernobyl accident. The inventory ratios of (239,240)Pu/(137)Cs were 0.041 and 0.025 in the western and eastern basins respectively, greater than the fallout ratio, 0.021, showing more efficient scavenging of (239,240)Pu in the water column and major sedimentation of (137)Cs in the eastern basin. Although areas with water depths of >2000 m constitute around 40% of the entire Mediterranean basin, the sediments in these regions only contained 2.7% of the (239,240)Pu and 0.95% of the (137)Cs deposited across the Sea in 2000. These data show that the accumulation of artificial radionuclides in deep Mediterranean environments is much lower than predicted by other studies from the analysis of continental shelf sediments.

Spatial and temporal distribution of heavy metal concentrations and enrichment in the southern Gulf of Mexico.

Trace element (As, Co, Cr, Cu, Ni, Pb, V and Zn) enrichment trends during the past century, were assessed in thirteen 210Pb-dated sediment cores from the southern Gulf of Mexico, with the purpose to evaluate the impact on the environment, and potentially on public health, of the offshore oil industry and of oil spills such as that of the Ixtoc1 well blowout in 1979. The trace element composition was quite homogeneous among cores; and the pre-industrial concentrations of Ba, Cr, Cu and Ni are naturally high in the region, as to reach levels of potential ecological concern. The influence of multiple and simultaneous processes (e.g. industrial activities, natural seeps, fluvial discharges) on the trace element concentrations is difficult to disentangle. Some cores suggested long-term preservation of putative oil spill traces, although it was not possible to attribute their origin. The Al-normalized redox element ratios, and the crude oil contamination ratio, suggested that these events occurred along almost four decades, and that the traces attributed to the Ixtoc1 spill were comparable to background conditions, most likely owing to active natural oil seeps in the area. In most cases there was a trend towards a lowering in the supply of trace elements; this might be associated with environmental controls in the region since the 1980s. This study highlights the relevance of using dated environmental archives to reconstruct the historical trends of trace metal contamination in areas where long-term environmental studies are scarce.

Mercury in sediment cores from the southern Gulf of Mexico: Preindustrial levels and temporal enrichment trends.

Spatial and temporal variability of mercury concentrations in sediments was evaluated in 210Pb-dated sediment cores from offshore and intertidal areas in the southern Gulf of Mexico. In offshore cores, mercury concentrations were comparable (11.2-69.2 ng g-1), and intermediate between concentrations in intertidal cores from the eastern (6.0-34.4 ng g-1) and the western (34.9-137.7 ng g-1) inlets of Términos Lagoon. The enrichment factor (EF) indicated minimal contamination (EF < 2) in most offshore cores, whereas in some intertidal cores steadily increasing mercury enrichment and fluxes were observed along the past century. No evidence of oil industry related mercury contamination was found, as the minor but increasing enrichment in intertidal cores is most likely related to land-derived sources such as catchment eroded soils and waste water runoff. Results highlight the importance to control catchment erosion and untreated sewage releases to reduce mercury loadings to the coastal zone.

Natural and anthropogenic oil impacts on benthic foraminifera in the southern Gulf of Mexico.

The Campeche Sound is the major offshore oil producing area in the Southern Gulf of Mexico (SGoM). To evaluate the impact of oil related activities in the ocean floor sediments, we analyzed the geochemical (major and trace element, organic carbon and hydrocarbon concentrations) and biological (benthic foraminifera) composition of 62 superficial sediment samples, from 13 to 1336 m water depth. Cluster and Factor analysis of all the variables indicate that their distribution patterns are mainly controlled by differences between the terrigenous and carbonate platforms in the SGoM. Benthic foraminiferal assemblages were abundant and diverse, and their distribution patterns are mainly determined by water depth and sedimentary environment. However, most of the abundant species are opportunistic and/or low-oxygen tolerant, and many of their tests show oil stains and infillings, characteristic of oil polluted locations, suggesting the environment has been modified by natural seepage or oil-related activities. To determine if these conditions are natural or anthropogenic in origin, pre - industrial settings should be studied. Organic carbon (Corg) content (0.6-2.9%) and total hydrocarbon concentrations (PAHs 1.0-29.5 µg kg-1) were usually higher around the oil platforms area, the natural hydrocarbon seeps ("chapopoteras") area and offshore rivers, but there is no accumulation of oil related trace elements in these areas. However, the comparison with international sediment quality benchmarks indicates that Cd, Cr and Ni concentrations are above the threshold effect level, and also As, Ba and Cu are above the probable effect level benchmarks, which indicate that these element concentrations might be of potential ecological concern. Comprehensive studies involving different proxies, and assessing pre-industrial conditions, must be undertaken before assessing environmental health of marine benthic ecosystems.

IAEA programme on the quality of marine radioactivity data.

Society's growing interest in environmental issues requires the production of reliable information for policy-makers, stakeholders and society in general. This information must be based on accurate data produced by qualified laboratories and data need to be comparable between numerous laboratories for joint assessments, e.g. in International Conventions. The Marine Environment Laboratories of the International Atomic Energy Agency has been providing Quality Assurance services to laboratories involved in marine radioactivity studies for the past 30 years. This has included training, organization of laboratory intercomparison exercises, production of Reference Materials (RMs) and more recently, production of Certified Reference Materials (CRMs) that comply with relevant ISO standards. Here, the overall process of Certification of Reference Materials is reviewed, past work summarized and future needs of marine radioactivity laboratories briefly discussed.

A new Certified Reference Material for radionuclides in Irish sea sediment (IAEA-385).

A new Certified Reference Material (CRM) for radionuclides in sediment (IAEA-385) is described and the results of the certification process are presented. Eleven radionuclides ((40)K, (137)Cs, (226)Ra, (228)Ra, (230)Th, (232)Th, (234)U, (238)U, (238)Pu, (239+240)Pu and (241)Am) have been certified and information mass activities with 95% confidence intervals are given for seven other radionuclides ((90)Sr, (210)Pb((210)Po), (235)U, (239)Pu, (240)Pu and (241)Pu). Results for less frequently reported radionuclides ((60)Co, (99)Tc, (134)Cs, (155)Eu, (224)Ra and (239)Np) and information on some activity and mass ratios are also reported. The CRM can be used for quality assurance/quality control of the analysis of radionuclides in sediment samples, for the development and validation of analytical methods and for training purposes.

Carbon burial and storage in tropical salt marshes under the influence of sea level rise.

Coastal vegetated habitats can be important sinks of organic carbon (Corg) and mitigate global warming by sequestering significant quantities of atmospheric CO2 and storing sedimentary Corg for long periods, although their Corg burial and storage capacity may be affected by on-going sea level rise and human intervention. Geochemical data from published 210Pb-dated sediment cores, collected from low-energy microtidal coastal wetlands in El Salvador (Jiquilisco Bay) and in Mexico (Salada Lagoon; Estero de Urias Lagoon; Sian Ka'an Biosphere Reserve) were revisited to assess temporal changes (within the last 100years) of Corg concentrations, storage and burial rates in tropical salt marshes under the influence of sea level rise and contrasting anthropization degree. Grain size distribution was used to identify hydrodynamic changes, and δ13C to distinguish terrigenous sediments from those accumulated under the influence of marine transgression. Although the accretion rate ranges in all sediment records were comparable, Corg concentrations (0.2-30%), stocks (30-465Mgha-1, by extrapolation to 1m depth), and burial rates (3-378gm-2year-1) varied widely within and among the study areas. However, in most sites sea level rise decreased Corg concentrations and stocks in sediments, but increased Corg burial rates. Lower Corg concentrations were attributed to the input of reworked marine particles, which contribute with a lower amount of Corg than terrigenous sediments; whereas higher Corg burial rates were driven by higher mass accumulation rates, influenced by increased flooding and human interventions in the surroundings. Corg accumulation and long-term preservation in tropical salt marshes can be as high as in mangrove or temperate salt marsh areas and, besides the reduction of Corg stocks by ongoing sea level rise, the disturbance of the long-term buried Corg inventories might cause high CO2 releases, for which they must be protected as a part of climate change mitigation efforts.

Plutonium and 137Cs in surface water of the South Pacific Ocean.

The present plutonium and 137Cs concentrations in South Pacific Ocean surface waters were determined. The water samples were collected in the South Pacific mid-latitude region (32.5 degrees S) during the BEAGLE expedition conducted in 2003-04 by JAMSTEC. 239,240Pu concentrations in surface seawater of the South Pacific were in the range of 0.5 to 4.1 mBq m(-3), whereas 137Cs concentrations ranged from 0.07 to 1.7 Bq m(-3). The observed 239,240Pu and 137Cs concentrations in the South Pacific were almost of the same level as those in the North Pacific subtropical gyre. The surface 239,240Pu in the South Pacific subtropical gyre showed larger spatial variations than 137Cs, as it may be affected by physical and biogeochemical processes. The 239,240Pu/137Cs activity ratios, which reflect biogeochemical processes in seawater, were generally smaller than that observed in global fallout, except for the most eastern station. The 239,240Pu/137Cs ratios in the South Pacific tend to be higher than that in the North Pacific. The relationships between anthropogenic radionuclides and oceanographic parameters such as salinity and nutrients were examined. The 137Cs concentrations in the western South Pacific (the Tasman Sea) and the eastern South Pacific were negatively correlated with the phosphate concentration, whereas there is no correlation between the 137Cs and nutrients concentrations in the South Pacific subtropical gyre. The mutual relationships between anthropogenic radionuclides and oceanographic parameters are important for better understanding of transport processes of anthropogenic radionuclides and their fate in the South Pacific.

Certified reference material for radionuclides in fish flesh sample IAEA-414 (mixed fish from the Irish Sea and North Sea).

A certified reference material (CRM) for radionuclides in fish sample IAEA-414 (mixed fish from the Irish Sea and North Seas) is described and the results of the certification process are presented. Nine radionuclides (40K, 137Cs, 232Th, 234U, 235U, 238U, 238Pu, 239+240Pu and 241Am) were certified for this material. Information on massic activities with 95% confidence intervals is given for six other radionuclides (90Sr, 210Pb(210Po), 226Ra, 239Pu, 240Pu 241Pu). Less frequently reported radionuclides (99Tc, 129I, 228Th, 230Th and 237Np) and information on some activity and mass ratios are also included. The CRM can be used for quality assurance/quality control of the analysis of radionuclides in fish sample, for the development and validation of analytical methods and for training purposes. The material is available from IAEA, Vienna, in 100 g units.

Characterization of the NIST seaweed Standard Reference Material.

The National Institute of Standards and Technology (NIST) Standard Reference Material (SRM) for seaweed was developed through an interlaboratory comparison with 24 participants from 16 countries. After evaluating different techniques to calculate certified values for the radionuclides, the median method was found to be the most representative technique. The certified values were provided for 13 radionuclides and information values were given for 15 more radionuclides. Results for the natural decay series showed disequilibrium in both the uranium and thorium series.

Combined environmental stress from shrimp farm and dredging releases in a subtropical coastal lagoon (SE Gulf of California).

Nutrient pollution causes environmental damages on aquatic ecosystems worldwide. Eutrophication produces impacts in coastal ecosystems, affecting biota and ecosystem services. The Urias coastal lagoon (SE Gulf of California) is a sub-tropical estuary under several environmental pressures such as nutrient inputs from shrimp farm effluents and dredging related to port operations, which can release substances accumulated in sediments. We assessed the water quality impacts caused by these activities and results showed that i) nitrogen was the limiting nutrient, ii) shrimp farm effluents increased particulate organic matter and chlorophyll a in the receiving stations, and iii) dredging activities increased nitrite and reduced dissolved oxygen concentrations. The co-occurrence of the shrimp farm releases and dredging activities was likely the cause of a negative synergistic effect on water quality which mainly decreases dissolved oxygen and increases nitrite concentrations. Coastal zone management should avoid the co-occurrence of these, and likely others, stressors in coastal ecosystems.

Historical trends of organochlorine pesticides in a sediment core from the Gulf of Batabanó, Cuba.

Sediments can be natural archives to reconstruct the history of pollutant inputs into coastal areas. This is important to improve management strategies and evaluate the success of pollution control measurements. In this work, the vertical distribution of organochlorine pesticides (DDTs, Lindane, HCB, Heptachlor, Aldrin and Mirex) was determined in a sediment core collected from the Gulf of Batabanó, Cuba, which was dated by using the (210)Pb dating method and validated with the (239,240)Pu fallout peak. Results showed significant changes in sediment accumulation during the last 40 years: recent mass accumulation rates (0.321 g cm(-2) yr(-1)) double those estimated before 1970 (0.15 g cm(-2) yr(-1)). This change matches closely land use change in the region (intense deforestation and regulation of the Colon River in the late 1970s). Among pesticides, only DDTs isomers, Lindane and HCB were detected, and ranged from 0.029 to 0.374 ng g(-1) dw for DDTs, from<0.006 to 0.05 ng g(-1) dw for Lindane and from<0.04 to 0.134 ng g(-1) dw for HCB. Heptachlor, Aldrin and Mirex were below the detection limits (∼0.003 ng g(-1)), indicating that these compounds had a limited application in the Coloma watershed. Pesticide contamination was evident since the 1970s. DDTs and HCB records showed that management strategies, namely the banning the use of organochlorine contaminants, led to a concentration decline. However, Lindane, which was restricted in 1990, can still be found in the watershed. According to NOAA guidelines, pesticides concentrations encountered in these sediments are low and probably not having an adverse effect on sediment dwelling organisms.

Use of tritium to predict soluble pollutants transport in Ebro River waters (Spain).

The Ebro River, in Northeast Spain, discharges into the Mediterranean Sea after flowing through several large cities and agricultural, mining and industrial areas. The Ascó nuclear power plant (NPP) is located in its lower section and comprises two pressurised water reactor units, from which low-level liquid radioactive waste is released to river waters under authority control. Tritium routinely released by the NPP was used as a radiotracer to determine the longitudinal dispersion coefficient and velocity of the river waters. Several field experiments, in co-ordination with the NPP, were carried out during 1991 and 1992. During each field experiment, the flow rate was kept constant by dams located upstream from the NPP. After each tritium release, water was sampled downstream at periodic intervals over several hours and tritium was measured with a low-background liquid scintillation counter. Velocity and dispersion coefficient were determined in river waters for several river discharges using an analytical, box-type and numerical approach to solve the one-dimensional advection-diffusion equation. The set of calibrated parameters was used to predict the displacement and dispersion of soluble pollutants in river waters. Velocity was determined as a function of river discharge and river slope, and dispersion coefficient was determined as a function of distance. Finally, sensitivity of the model predictions was studied and uncertainties of the fitted parameters were estimated.

Perturbation in the 240Pu/239Pu global fallout ratio in local sediments following the nuclear accidents at Thule (Greenland) and Palomares (Spain).

It is well established that the main source of the plutonium found in marine sediments throughout the Northern Hemisphere is global stratospheric fallout, characterized by a typical 240Pu/239Pu atom ratio of approximately 0.18. Measurement of perturbations in this ratio at various sites which had been subjected to close-in fallout, mainly from surface-based testing (e.g. Bikini Atoll, Nevada test site, Mururoa Atoll), has confirmed the feasibility of using this ratio to distinguish plutonium from different fallout sources. In the present study, the 240Pu/239Pu ratio has been examined in samples of sediment (and soil) collected at Thule (Greenland) and Palomares (Spain), where accidents involving the release and dispersion of plutonium from fractured nuclear weapons occurred in 1968 and 1966, respectively. The 240Pu/239Pu ratio was measured by high-resolution alpha spectrometry and spectral deconvolution, and confirmed in the case of the most active samples by high-resolution X-ray spectrometry. Only samples which displayed plutonium heterogeneities, i.e. hot particles or concentrations well in excess (at least two orders of magnitude) of those expected from global fallout, were selected for analysis. The analytical results showed that at Thule the mean 240Pu/239Pu atom ratio was 0.033 +/- 0.004 (n = 4), while at Palomares the equivalent ratio appeared to be significantly higher at 0.056 +/- 0.003 (n = 4). Both ratios are indicative of low burn-up plutonium and are consistent with those reported for weapons-grade plutonium. It is noteworthy that the mean 238Pu/239Pu activity ratio in the Thule samples, at 0.0150 +/- 0.0017 (n = 4), was also lower than that measured in the Palomares samples, namely, 0.0275 +/- 0.0012 (n = 4). The 241Pu/239Pu ratios were similarly different. Finally, the data show, in contrast to Palomares, that not all of the samples from the Thule accident site were contaminated with plutonium of identical isotopic composition.

A rapid method for the simultaneous determination of gross alpha and beta activities in water samples using a low background liquid scintillation counter.

The radiological examination of water requires a rapid screening technique that permits the determination of the gross alpha and beta activities of each sample in order to decide if further radiological analyses are necessary. In this work, the use of a low background liquid scintillation system (Quantulus 1220) is proposed to simultaneously determine the gross activities in water samples. Liquid scintillation is compared to more conventional techniques used in most monitoring laboratories. In order to determine the best counting configuration of the system, pulse shape discrimination was optimized for 6 scintillant/vial combinations. It was concluded that the best counting configuration was obtained with the scintillation cocktail Optiphase Hisafe 3 in Zinsser low diffusion vials. The detection limits achieved were 0.012 Bq L-1 and 0.14 Bq L-1 for gross alpha and beta activity respectively, after a 1:10 concentration process by simple evaporation and for a counting time of only 360 min. The proposed technique is rapid, gives spectral information, and is adequate to determine gross activities according to the World Health Organization (WHO) guideline values.

Trace element fluxes and natural potential risks from 210Pb-dated sediment cores in lacustrine environments at the Central Mexican Plateau.

The accumulation, enrichment and provenance of selected trace metals (Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, V and Zn) were studied in sediment cores collected from three lakes located in the Central Mexican Plateau, selected on the basis of their contrasting degree of urbanization: Santa Elena Lake, in a rural and remote area; El Tule Lake, in a rural and slightly urbanized area; and Chapala Lake, in a highly urbanized area. Grain size, magnetic susceptibility and sedimentary constituents such as organic carbon, calcium carbonate, as well as major (Al, Fe, Mn) and minor (Ca, Li, Rb, Sr, Th) elements were analyzed to explain the concentration trends of trace metals. Factor analysis (FA) was used to assess the provenance of the trace elements. The highest metal enrichment factor (EF) above natural concentration levels was found at Chapala Lake for Ag (EF = 3.9), although other trace element EF in all lakes was <2.0, indicating slight contamination. However, the concentration levels of Cr and Ni in all lakes, Hg and Zn in Chapala Lake, Cu in El Tule Lake and As in Santa Elena Lake were above international benchmarks for which adverse effects are expected to occur frequently, even for those metals only slightly enriched (e.g. As, Cr). Through FA, the terrigenous contribution was identified as the most important source of trace metals to the three lakes, most likely related to deforestation and erosion of the surrounding areas, followed by atmospheric transport of volcanic ashes, rather than to direct sources.